| Metadata | Details |
|---|
| Publication Date | 2023-10-24 |
| Journal | Materials |
| Authors | JÄdrzej Kozak, Katarzyna TyszczukâRotko, Aleksy Keller, Magdalena WĂłjciak, Ireneusz Sowa |
| Institutions | Medical University of Lublin, Maria Curie-SkĹodowska University |
| Citations | 4 |
| Analysis | Full AI Review Included |
- Core Achievement: Development of an electrochemically activated Screen-Printed Boron-Doped Diamond Electrode (aSPBDDE) for the rapid and highly sensitive determination of curcumin (CCM) using Differential Pulse Adsorptive Stripping Voltammetry (DPAdSV).
- Ultra-Low Detection Limit: The optimized procedure achieved an extremely low Limit of Detection (LOD) of 5.0 x 10-13 mol/L, significantly surpassing most published voltammetric and chromatographic methods for CCM analysis.
- Performance Enhancement: Electrochemical activation (5 CV scans in 0.1 mol/L NaOH) reduced the charge transfer resistance (Rct) from 286.5 to 105 Ί cm2, resulting in a nearly twofold amplification of the CCM analytical signal.
- Matrix Tolerance: The high sensitivity allows for extreme sample dilution (up to 2,000,000-fold for extracts), effectively minimizing matrix interference from complex food samples.
- Validation and Accuracy: Results obtained for food products (turmeric extract, herbal tea, immune shot) showed excellent agreement with the reference method (UHPLC-ESI/MS), with a maximum Relative Error of 8.8%.
- Sensor Novelty: This study marks the first successful application of a screen-printed sensor for the quantitative determination of CCM, offering a simple, fast, and cost-effective analytical tool.
| Parameter | Value | Unit | Context |
|---|
| Limit of Detection (LOD) | 5.0 x 10-13 | mol/L | Optimized DPAdSV procedure |
| Limit of Quantification (LOQ) | 1.7 x 10-12 | mol/L | Optimized DPAdSV procedure |
| Linear Range (Overall) | 2.0 x 10-12 to 2.0 x 10-8 | mol/L | Total concentration range tested |
| Optimal Supporting Electrolyte | 0.025 | mol/L | PBS (pH 2.6) |
| Accumulation Potential (Eacc) | 0.3 | V | DPAdSV parameter |
| Accumulation Time (tacc) | 90 | s | DPAdSV parameter |
| Scan Rate (v) | 150 | mV/s | DPAdSV parameter |
| Amplitude (ÎEA) | 100 | mV | DPAdSV parameter |
| Modulation Time (tm) | 10 | ms | DPAdSV parameter |
| Charge Transfer Resistance (Rct) (SPBDDE) | 286.5 | Ί cm2 | Before electrochemical activation |
| Charge Transfer Resistance (Rct) (aSPBDDE) | 105 | Ί cm2 | After electrochemical activation |
| Repeatability (RSD) | 4.97 | % | 1.0 x 10-9 mol/L CCM (n=10) |
| Reproducibility (RSD) | 3.85 | % | Across three separate sensors |
| Turmeric Extract Dilution Factor | 2,000,000-fold | N/A | Used for voltammetric analysis |
- Electrode Selection and Configuration: Screen-printed sensors featuring a boron-doped diamond working electrode, a silver pseudo-reference electrode, and a carbon counter electrode were utilized.
- Electrochemical Activation Recipe: The SPBDDE was activated in a solution of 0.1 mol/L NaOH by performing five consecutive Cyclic Voltammetric (CV) scans in the potential range of 0-2 V, at a scan rate of 100 mV/s. This process removes organic binder components, increasing surface roughness and reducing Rct.
- Supporting Electrolyte Optimization: The optimal medium was determined to be 0.025 mol/L Phosphate-Buffered Saline (PBS) at pH 2.6, which maximized the CCM oxidation peak current and stability.
- Adsorption Confirmation: Differential capacity-potential curves (recorded at 200 Hz) confirmed that the CCM electro-oxidation mechanism is controlled by adsorption onto the aSPBDDE surface.
- DPAdSV Optimization: Key parameters were optimized for maximum signal intensity and repeatability:
- Accumulation Potential (Eacc): 0.3 V.
- Accumulation Time (tacc): 90 s (chosen for speed, though signal increased up to 600 s).
- Scan Rate (v): 150 mV/s.
- Amplitude (ÎEA): 100 mV.
- Validation Method: Analytical results were cross-validated using Ultra-High-Performance Liquid Chromatography coupled with Electrospray Ionization Mass Spectrometry (UHPLC-ESI/MS) in negative mode, using 45% acetonitrile/water (0.05% formic acid) mobile phase at 0.2 mL/min.
- Portable Food Quality Assurance: The use of low-cost, screen-printed sensors enables the development of portable, handheld voltammetric analyzers for rapid, on-site quality control of spices, supplements, and functional foods containing curcumin.
- High-Sensitivity Trace Analysis: The ultra-low LOD (5.0 x 10-13 mol/L) is critical for monitoring trace levels of polyphenols and antioxidants in complex matrices, including biological fluids (plasma, urine) and highly diluted food extracts.
- BDD Sensor Manufacturing: The demonstrated success of the activated screen-printed BDD electrode validates the use of BDD ink technology for mass-produced, high-performance electrochemical sensors, leveraging BDDâs chemical inertness and wide potential window.
- Electrochemical Sensor Activation Systems: The established electrochemical activation protocol (CV in NaOH) provides a simple, scalable method for enhancing the performance of screen-printed electrodes by optimizing surface morphology and conductivity.
- Antioxidant and Pharmaceutical Screening: The methodology can be adapted for the rapid screening and quantification of other electroactive polyphenols and pharmaceutical compounds in complex samples, replacing slower, more expensive chromatographic techniques.
View Original Abstract
Due to a great interest in the beneficial properties of polyphenolic antioxidant curcumin (CCM), sensitive and accurate methods for determining CCM are needed. The purpose of our research was to develop a very simple, fast, and sensitive differential pulse adsorptive stripping voltammetric (DPAdSV) procedure using an electrochemically activated screen-printed boron-doped diamond electrode (aSPBDDE) for the determination of CCM. The activation of the SPBDDE was accomplished in a solution of 0.1 mol/L NaOH by performing five cyclic voltammetric scans in the range of 0-2 V, at ν of 100 mV/s. The changes in surface morphology and the reduction of the charge transfer resistance due to the activation of the electrode resulted in the amplification of the CCM analytical signal on the aSPBDDE. As a result, an extremely sensitive measurement tool was formed, which under optimized conditions (0.025 mol/L PBS of pH = 2.6, Eacc of 0.3 V, tacc of 90 s, ÎEA of 100 mV, ν of 150 mV/s, and tm of 10 ms) allowed us to obtain a limit of detection (LOD) of 5.0 Ă 10â13 mol/L. The aSPBDDE has proven to be a highly effective tool for the direct determination of CCM in food samples with high accuracy and precision. The results are in agreement with those obtained using ultra-high-performance liquid chromatography coupled with mass spectrometry and electrospray ionization (UHPLC-ESI/MS).
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